EP0370909A1 - Process for the conversion of natural gas or of light alkanes into unsaturated hydrocarbons - Google Patents
Process for the conversion of natural gas or of light alkanes into unsaturated hydrocarbons Download PDFInfo
- Publication number
- EP0370909A1 EP0370909A1 EP89403234A EP89403234A EP0370909A1 EP 0370909 A1 EP0370909 A1 EP 0370909A1 EP 89403234 A EP89403234 A EP 89403234A EP 89403234 A EP89403234 A EP 89403234A EP 0370909 A1 EP0370909 A1 EP 0370909A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bed
- plasma
- hydrogen
- natural gas
- particles
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S585/00—Chemistry of hydrocarbon compounds
- Y10S585/929—Special chemical considerations
- Y10S585/943—Synthesis from methane or inorganic carbon source, e.g. coal
Definitions
- the present invention relates to a process for converting natural gas or light alkane (s) into unsaturated hydrocarbons and more particularly to a conversion process with supply of electrical energy applied in particular in the chemical and energy industries.
- a representative process is the Hüls process which allows the conversion of hydrocarbons such as methane to unsaturated hydrocarbons and in particular to acetylene. This process involves passing methane through an electric arc and then separating the products obtained. However, this process has the disadvantage of forming a very large amount of carbon black.
- the hydrogen plasma provides the energy necessary for the methane conversion reaction, which is an endothermic reaction. This energy is brought in situ by the plasma gases without the intermediary of a wall.
- the plasma is a source of energy in the methane conversion reaction, it still has disadvantages because its temperature is too high for the envisaged reaction.
- the methane brought to a temperature above 1200 ° C. is broken down by a succession of dehydrogenation and cyclization reactions into a mixture of polyaromatic substances leading to carbon black.
- the object of the invention is a method which does not present the difficulties and drawbacks of the known methods.
- the invention is characterized in that a fluidized bed of particles of refractory and advantageously catalytic material is created inside a reaction space and that a plasma is introduced of a gas containing hydrogen and natural gas or the light alkane (s) in the bed so that it quench the reaction medium and catalyze the conversion reaction.
- the bed of particles is fluidized by a gas stream of fluidization advantageously containing hydrogen.
- the gaseous fluidization stream contains hydrogen and argon.
- the natural gas or the light alkane (s) is introduced into the bed with the gaseous fluidization stream and the light alkane is methane.
- the fluidizing hydrogen and the methane are introduced into the bed in a hydrogen / methane proportion ranging from 0.5 to 10 and preferably from 2 to 5.
- the gaseous fluidization stream is preheated upstream of the bed to a temperature between 50 ° C and 500 ° C and preferably between 150 ° C and 350 ° C.
- a plasma is introduced containing at least 10% hydrogen and which may contain argon.
- the bed consists of particles of a material chosen in particular from the group consisting of oxides, carbides, nitrides and borides.
- the particles produce a catalytic effect.
- the bed also contains a catalyst.
- the conversion reaction is carried out in the bed at a temperature between 500 ° C and 1200 ° C and preferably between 500 ° C and 800 ° C.
- the method of the invention is implemented using a device of the type shown in the appended figure and comprising an enclosure 1 comprising at its bottom means 2 for injecting a gaseous stream of fluidization, means for leaving the latter (not shown) and containing a mass of particles of a material intended to form a fluidized bed 3, and a plasma torch 6 of a gas containing hydrogen, suitable for introducing the plasma inside the enclosure in the fluidized particle bed.
- the plasma torch is connected to a wall of the enclosure so that the plasma is introduced into the fluidized bed.
- the angle of introduction of the torch into the enclosure can be varied from 0 ° to 90 °.
- the angle of introduction of the torch is 20 ° relative to the horizontal section of the enclosure.
- this torch consists of two concentric tubes of silica, with an external diameter of 30 mm, surrounded by five hollow inductive turns of copper cooled by water, traversed by an electric current of high frequency.
- the internal wall of the enclosure 1 is for example made of refractory alumina 4 mm thick, insulated by a layer of 20 mm of porous bricks. The whole is covered with glass wool and an asbestos ribbon.
- the dimensions of the enclosure larger than those of the plasma avoid direct contact of the walls with the hot zone of the plasma.
- the enclosure has a pyramidal zone in which the particles are suspended and thermocouples (not shown) are installed in the enclosure to measure the temperature of the fluidized bed.
- a hemispherical lapping (not shown) installed on one of the sides of the enclosure, allows the introduction of the plasma thus treating all the particles.
- the means 2 for injecting the gaseous fluidization stream comprise for example a 40 mm opaque silica tube surrounded by a heating tape and filled with refractory balls, this system allows the preheating of the gases and a thermocouple (not shown) is provided. in the tube to control the temperature of the fluidizing gases.
- the evacuation tube 5 is for example constituted by a quartz tube 85 mm in diameter and 500 mm in length and thermocouples (not shown) are installed in this tube to measure the temperature of the gas stream passing through it.
- the outlet of this tube can be connected to a water heat exchanger (not shown) in which the reaction mixture is cooled before being taken for analysis.
- the bed consists of particles of a material chosen in particular from the group consisting of oxides, carbides, nitrides, and borides.
- oxides aluminum Al2O3 magnesium MgO calcium
- C - oxides aluminum Al2O3 magnesium MgO calcium
- other mixed oxides - carbides silicon SiC of thorium ThC boron B
- these must be refractory because the particles of the bed must be able to withstand high temperatures since they are in contact with the plasma jet.
- the particles in the bed can themselves act as a catalyst and it is also possible to add another catalyst to them.
- the particles of the bed are made to fluidize into a gushing bed by the flow of a gaseous stream of fluidization formed mainly of hydrogen or of a mixture of hydrogen and argon introduced into the 'enclosure 1 using the injection means 2 and the natural gas or light alkane (s) to be converted are introduced into the thus fluidized bed.
- the natural gas or the light alkane (s) is introduced into the fluidized bed with the gaseous fluidization stream.
- the optimum amount of fluidizing hydrogen is determined so as to minimize the formation of carbon black.
- the fluidizing gases are preheated upstream of the bed, in the tube 2, to a temperature between 50 ° C and 500 ° C and preferably between 150 ° C and 350 ° C.
- the plasma torch 6 injects a hydrogen plasma, which may contain argon and containing at least 10% hydrogen, into the fluidized particle bed where a homogeneous transfer of heat takes place between the plasma and fluidized bed , thus making it possible to carry out a conversion reaction in the presence of radical hydrogen at an adjusted temperature which remains notably lower than that of plasma, which therefore minimizes the formation of carbon black.
- a hydrogen plasma which may contain argon and containing at least 10% hydrogen
- a fluidized bed in the process according to the invention has significant advantages for the following reasons: - its heat transfer properties allow efficient quenching of the plasma; - Its viscosity substantially equal to that of the plasma ensures a very good mixture between it and the fluidized bed; and - its possible catalytic properties can ensure the direct transformation of the product or products to be converted into unsaturated hydrocarbons.
- the plasma torch operates at a frequency of 5 MHz for a power of 4.4 kW.
- the injection angle is 20 °.
- the plasma gases introduced are argon, at a flow rate of 30 l / min and hydrogen at a flow rate of 5 l / min.
- the bed is made of alumina particles (650g) of 300 microns in average diameter. The particles of the bed are put in fluidization by a mixture of methane, hydrogen and argon. By adjusting the flow rate of these three gases, the residence time of the methane in the reactor is adjusted. Good fluidization is obtained for a total flow of between 15 l / min and 40 l / min.
- the optimal amount of hydrogen fluidization is determined relative to that of methane so as to minimize the formation of carbon black.
- This ratio is between 0.5 and 10 and preferably between 2 and 5.
- the fluidization gases are preheated to a temperature between 50 and 500 ° C, preferably between 150 ° C and 350 ° C.
- the plasma gas and fluidization flow rates are measured and regulated using mass flow meters.
- Thermocouples are installed to measure the temperature of the fluidizing gases upstream of the enclosure, the wall of the enclosure, the fluidized bed and the temperatures in the tube 5.
- the temperature of the fluidized bed is chosen as the reference temperature since on the one hand it characterizes the efficiency of the quenching and on the other hand because the conversion reaction takes place in the fluidized bed.
- the analysis of the products is carried out by gas chromatography.
- Examples 1 to 3 were carried out under identical fluidization conditions but at three different temperatures. The results show that the amount of carbon black formed increases very rapidly with temperature. It emerges from these results that temperature control is essential and we therefore understand the advantage of soaking the plasma.
- Example 4 was carried out at a temperature of 500 ° C. Note that the conversion rate of CH4 at this temperature is only 9%. Consequently a temperature of about 500 ° C constitutes the lower limit for the conversion of methane.
- Examples 5 and 6 were carried out at the same temperature but with a different fluidization flow. There is an increase in the conversion rate when the flow rate of the fluidizing gas decreases, that is to say when the residence time of the methane increases. The control of this important parameter can therefore be done easily.
- Example 8 was carried out to observe the specific role of plasma which is to provide in high concentration radical species. To do this, a simple experiment was carried out which consists in stopping the torch and immediately analyzing the reaction mixture. Note that at the same temperature but without the plasma, the methane conversion rate is negligible.
- Methane conversion is defined by the ratio of the amount of methane converted to the total amount of methane introduced. It is calculated as follows: with (X) molar concentration of component X in the reaction mixture, given by chromatographic analysis.
- C2 selectivity is the ratio of the quantity of C2 products obtained by the quantity of conversion products. It is calculated as follows:
- the yield in C2 is defined by the ratio of the quantity of C2 products obtained by the quantity of methane introduced. It is calculated as follows
- the invention is in no way limited to the embodiments described and illustrated which are given only by way of example.
- the products to be converted could be introduced into the fluidized bed, differently from the example shown, that is to say separately from the fluidization gas, at any suitable location provided that the quenching of the plasma by the bed is respected. fluidized.
- the plasma used can be produced in any manner, in particular by blown or transferred electric arc or even by induction.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Industrial Gases (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
La présente invention se rapporte à un procédé de conversion de gaz naturel ou d'alcane (s) léger (s) en hydrocarbures insaturés et plus particulièrement à un procédé de conversion avec apport d'énergie électrique appliqué notamment dans les industries chimiques et énergétiques.The present invention relates to a process for converting natural gas or light alkane (s) into unsaturated hydrocarbons and more particularly to a conversion process with supply of electrical energy applied in particular in the chemical and energy industries.
Il existe actuellement des procédés de conversion avec apport d'énergie électrique. Un procédé représentatif est le procédé Hüls qui permet la conversion d'hydrocarbures tels que le méthane en hydrocarbures insaturés et notamment en acétylène. Ce procédé consiste à faire passer du méthane dans un arc électrique puis à séparer les produits obtenus. Cependant ce procédé a pour inconvénient de former une quantité très importante de noir de carbone.There are currently conversion processes with the supply of electrical energy. A representative process is the Hüls process which allows the conversion of hydrocarbons such as methane to unsaturated hydrocarbons and in particular to acetylene. This process involves passing methane through an electric arc and then separating the products obtained. However, this process has the disadvantage of forming a very large amount of carbon black.
Aussi, une amélioration a été proposée en utilisant un plasma d'hydrogène. Le plasma d'hydrogène permet d'apporter l'énergie nécessaire à la réaction de conversion du méthane, qui est une réaction endothermique. Cette énergie est apportée in situ par les gaz plasmagènes sans l'intermédiaire d'une paroi. Mais si le plasma est une source d'énergie dans la réaction de conversion du méthane il présente encore des inconvénients car sa température est trop importante pour la réaction envisagée. En effet, le méthane porté à une température supérieure à 1200°C se décompose par une succession de réaction de déshydrogénations et de cyclisations en un mélange de substances polyaromatiques conduisant au noir de carbone.Also, an improvement has been proposed using a hydrogen plasma. The hydrogen plasma provides the energy necessary for the methane conversion reaction, which is an endothermic reaction. This energy is brought in situ by the plasma gases without the intermediary of a wall. However, if the plasma is a source of energy in the methane conversion reaction, it still has disadvantages because its temperature is too high for the envisaged reaction. In fact, the methane brought to a temperature above 1200 ° C. is broken down by a succession of dehydrogenation and cyclization reactions into a mixture of polyaromatic substances leading to carbon black.
Ces procédés ne sont donc pas complètement satisfaisants car ils impliquent une formation trop importante de noir de carbone de qualité non contrôlée qui devient donc un sous-produit difficilement valorisable.These methods are therefore not completely satisfactory since they involve too much black formation. of uncontrolled quality carbon which therefore becomes a difficult-to-recover by-product.
L'invention a pour but un procédé qui ne présente pas les difficultés et les inconvénients des procédés connus.The object of the invention is a method which does not present the difficulties and drawbacks of the known methods.
Pour atteindre ce but, l'invention est caractérisée en ce que l'on créé à l'intérieur d'un espace de réaction un lit fluidisé de particules d'un matériau réfractaire et avantageusement catalytique et en ce que l'on introduit un plasma d'un gaz contenant de l'hydrogène et le gaz naturel ou le ou les alcanes légers dans le lit de façon que celui-ci effectue une trempe du milieu réactionnel et catalyse la réaction de conversion.To achieve this object, the invention is characterized in that a fluidized bed of particles of refractory and advantageously catalytic material is created inside a reaction space and that a plasma is introduced of a gas containing hydrogen and natural gas or the light alkane (s) in the bed so that it quench the reaction medium and catalyze the conversion reaction.
Selon une caractéristique de l'invention, le lit de particules est fluidisé par un courant gazeux de fluidisation contenant avantageusement de l'hydrogène.According to a characteristic of the invention, the bed of particles is fluidized by a gas stream of fluidization advantageously containing hydrogen.
Selon encore une autre caractéristique de l'invention, le courant gazeux de fluidisation contient de l'hydrogène et de l'argon.According to yet another characteristic of the invention, the gaseous fluidization stream contains hydrogen and argon.
Selon un mode de réalisation préférentiel de l'invention, le gaz naturel ou le ou les alcanes légers est introduit dans le lit avec le courant gazeux de fluidisation et l'alcane léger est le méthane. L'hydrogène de fluidisation et le méthane sont introduits dans le lit en une proportion hydrogène/méthane allant de 0,5 à 10 et de préférence de 2 à 5.According to a preferred embodiment of the invention, the natural gas or the light alkane (s) is introduced into the bed with the gaseous fluidization stream and the light alkane is methane. The fluidizing hydrogen and the methane are introduced into the bed in a hydrogen / methane proportion ranging from 0.5 to 10 and preferably from 2 to 5.
Selon une autre caractéristique de l'invention, le courant gazeux de fluidisation est préchauffé en amont du lit à une température comprise entre 50°C et 500°C et de préférence entre 150°C et 350°C.According to another characteristic of the invention, the gaseous fluidization stream is preheated upstream of the bed to a temperature between 50 ° C and 500 ° C and preferably between 150 ° C and 350 ° C.
Selon une particularité du procédé de l'invention, on introduit un plasma contenant au moins 10% d'hydrogène et pouvant contenir de l'argon.According to a feature of the process of the invention, a plasma is introduced containing at least 10% hydrogen and which may contain argon.
Selon une autre particularité de l'invention, le lit est constitué de particules d'un matériau choisi notamment dans le groupe consistant en oxydes, carbures, nitrures et borures.According to another feature of the invention, the bed consists of particles of a material chosen in particular from the group consisting of oxides, carbides, nitrides and borides.
Selon une autre particularité de l'invention, les particules produisent un effet catalytique.According to another feature of the invention, the particles produce a catalytic effect.
Selon encore une autre particularité de l'invention, le lit contient de plus un catalyseur.According to yet another feature of the invention, the bed also contains a catalyst.
La réaction de conversion est réalisée dans le lit à une température comprise entre 500°C et 1200°C et de préférence entre 500°C et 800°C.The conversion reaction is carried out in the bed at a temperature between 500 ° C and 1200 ° C and preferably between 500 ° C and 800 ° C.
L'invention sera mieux comprise et d'autres buts, caractéristiques, détails et avantages de celle-ci apparaîtront plus clairement au cours de la description explicative qui va suivre faite en référence à la figure unique représentant un schéma d'un mode de réalisation préférentiel de l'invention.The invention will be better understood and other objects, characteristics, details and advantages thereof will appear more clearly during the explanatory description which follows, made with reference to the single figure representing a diagram of a preferred embodiment. of the invention.
Le procédé de l'invention est mis en oeuvre à l'aide d'un dispositif du type de celui représenté à la figure annexée et comprenant une enceinte 1 comportant au niveau de son fond des moyens d'injection 2 d'un courant gazeux de fluidisation, des moyens de sortie de ce dernier (non représentés) et contenant une masse de particules d'un matériau destinées à former un lit fluidisé 3, et une torche à plasma 6 d'un gaz contenant de l'hydrogène, adaptée pour introduire le plasma à l'intérieur de l'enceinte dans le lit de particules fluidisé.The method of the invention is implemented using a device of the type shown in the appended figure and comprising an enclosure 1 comprising at its bottom means 2 for injecting a gaseous stream of fluidization, means for leaving the latter (not shown) and containing a mass of particles of a material intended to form a fluidized
Il est prévu un tube d'évacuation 5 relié à la sortie de l'enceinte.There is an evacuation tube 5 connected to the outlet of the enclosure.
La torche à plasma est raccordée au niveau d'une paroi de l'enceinte de façon que le plasma soit introduit dans le lit fluidisé. On peut faire varier l'angle d'introduction de la torche dans l'enceinte de 0° à 90°. De préférence, l'angle d'introduction de la torche est de 20° par rapport à la section horizontale de l'enceinte. Typiquement cette torche est constituée de deux tubes concentriques en silice, d'un diamètre extérieur de 30 mm, entourés de cinq spires inductives creuses en cuivre refroidies à l'eau, parcourues par un courant électrique de fréquence élevée.The plasma torch is connected to a wall of the enclosure so that the plasma is introduced into the fluidized bed. The angle of introduction of the torch into the enclosure can be varied from 0 ° to 90 °. Preferably, the angle of introduction of the torch is 20 ° relative to the horizontal section of the enclosure. Typically this torch consists of two concentric tubes of silica, with an external diameter of 30 mm, surrounded by five hollow inductive turns of copper cooled by water, traversed by an electric current of high frequency.
La paroi interne de l'enceinte 1 est par exemple en alumine réfractaire de 4 mm d'épaisseur, calorifugée par une couche de 20 mm de briques poreuses. L'ensemble est recouvert de laine de verre et d'un ruban d'amiante. Les dimensions de l'enceinte plus importantes que celles du plasma évitent le contact direct des parois avec la zone chaude du plasma. L'enceinte comporte une zone pyramidale dans laquelle les particules sont mises en suspension et des thermocouples (non représentés) sont installées dans l'enceinte pour mesurer la température du lit fluidisé. Un rodage hémisphérique (non représenté) installé sur l'un des côtés de l'enceinte, permet l'introduction du plasma traitant ainsi l'ensemble des particules.The internal wall of the enclosure 1 is for example made of refractory alumina 4 mm thick, insulated by a layer of 20 mm of porous bricks. The whole is covered with glass wool and an asbestos ribbon. The dimensions of the enclosure larger than those of the plasma avoid direct contact of the walls with the hot zone of the plasma. The enclosure has a pyramidal zone in which the particles are suspended and thermocouples (not shown) are installed in the enclosure to measure the temperature of the fluidized bed. A hemispherical lapping (not shown) installed on one of the sides of the enclosure, allows the introduction of the plasma thus treating all the particles.
Les moyens d'injection 2 du courant gazeux de fluidisation comprennent par exemple un tube de silice opaque de 40 mm entouré d'un ruban chauffant et rempli de billes réfractaires, ce sytème permet le préchauffage des gaz et un thermocouple (non représenté) est prévu dans le tube pour contrôler la température des gaz de fluidisation.The means 2 for injecting the gaseous fluidization stream comprise for example a 40 mm opaque silica tube surrounded by a heating tape and filled with refractory balls, this system allows the preheating of the gases and a thermocouple (not shown) is provided. in the tube to control the temperature of the fluidizing gases.
Le tube d'évacuation 5 est par exemple constitué par un tube de quartz de 85 mm de diamètre et de 500 mm de longueur et des thermocouples (non représentés) sont installés dans ce tube pour mesurer la température de courant gazeux le traversant. La sortie de ce tube peut être reliée à un échangeur thermique à eau (non représenté) dans lequel le mélange réactionnel est refroidi avant d'être prélevé pour analyse.The evacuation tube 5 is for example constituted by a quartz tube 85 mm in diameter and 500 mm in length and thermocouples (not shown) are installed in this tube to measure the temperature of the gas stream passing through it. The outlet of this tube can be connected to a water heat exchanger (not shown) in which the reaction mixture is cooled before being taken for analysis.
Le lit est constitué de particules d'un matériau choisi notamment dans le groupe consistant en oxydes, carbures, nitrures, et borures. On peut en dresser à titre d'exemples la liste suivante :
- oxydes
d'aluminium Al₂O₃
de magnésium MgO
de calcium CaO
de béryllium BeO
de cérium CeO
de thorium ThO₂
d'hafnium HfO₂
de lanthane La₂O₃
et autres oxydes mixtes
- carbures
de silicium SiC
de thorium ThC
de bore B₄C
- nitrures
de bore BN
d'hafniumm HfN
de zirconium ZrN
- borures
de thorium ThB₄
de niobium NbB₂
de zirconium ZrB₂
- carbone (graphite) CThe bed consists of particles of a material chosen in particular from the group consisting of oxides, carbides, nitrides, and borides. The following list can be used as examples:
- oxides
aluminum Al₂O₃
magnesium MgO
calcium CaO
BeO beryllium
CeO cerium
ThO₂ thorium
hafnium HfO₂
by lanthanum La₂O₃
and other mixed oxides
- carbides
silicon SiC
of thorium ThC
boron B₄C
- nitrides
boron BN
Hfniumm HfN
ZrN zirconium
- borides
ThB₄ thorium
NobB₂ niobium
ZrB₂ zirconium
- carbon (graphite) C
Quelle que soit la nature des matériaux utilisés, ceux-ci doivent être réfractaires car les particules du lit doivent pouvoir résister à des températures élevées puisqu'elles sont en contact avec le jet de plasma. Les particules du lit peuvent elles même jouer le rôle de catalyseur et il est également possible de leur adjoindre un autre catalyseur.Whatever the nature of the materials used, these must be refractory because the particles of the bed must be able to withstand high temperatures since they are in contact with the plasma jet. The particles in the bed can themselves act as a catalyst and it is also possible to add another catalyst to them.
Il faut bien comprendre que le mot "catalyseur" est pris dans son sens large c'est-à-dire que les particules peuvent accélérer certaines réactions souhaitées ou inhiber certaines réactions non souhaitées comme la formation de noir de carbone ou coke.It should be understood that the word "catalyst" is taken in its broad sense, that is to say that the particles can accelerate certain desired reactions or inhibit certain undesired reactions such as the formation of carbon black or coke.
Dans le procédé de la présente invention, les particules du lit sont mises en fluidisation en un lit jaillissant par le débit d'un courant gazeux de fluidisation formé principalement d'hydrogène ou d'un mélange d'hydrogène et d'argon introduit dans l'enceinte 1 à l'aide des moyens d'injection 2 et on introduit dans le lit ainsi fluidisé le gaz naturel ou le ou les alcanes légers devant être convertis. De préférence, comme représenté dans le dispositif de la figure, le gaz naturel ou le ou les alcanes légers est introduit dans le lit fluidisé avec le courant gazeux de fluidisation. On détermine la quantité optimale d'hydrogène de fluidisation de façon à minimiser la formation de noir de carbone. Les gaz de fluidisation sont préchauffés en amont du lit, dans le tube 2, à une température comprise entre 50°C et 500°C et de préférence entre 150°C et 350°C.In the process of the present invention, the particles of the bed are made to fluidize into a gushing bed by the flow of a gaseous stream of fluidization formed mainly of hydrogen or of a mixture of hydrogen and argon introduced into the 'enclosure 1 using the injection means 2 and the natural gas or light alkane (s) to be converted are introduced into the thus fluidized bed. Preferably, as shown in the device of the figure, the natural gas or the light alkane (s) is introduced into the fluidized bed with the gaseous fluidization stream. The optimum amount of fluidizing hydrogen is determined so as to minimize the formation of carbon black. The fluidizing gases are preheated upstream of the bed, in the tube 2, to a temperature between 50 ° C and 500 ° C and preferably between 150 ° C and 350 ° C.
La torche à plasma 6 injecte un plasma d'hydrogène, pouvant contenir de l'argon et contenant au moins 10% d'hydrogène, dans le lit de particules fluidisé où s'effectue un transfert homogène de la chaleur entre le plasma et lit fluidisé, permettant ainsi la réalisation d'une réaction de conversion en présence d'hydrogène radicalaire à une température ajustée qui demeure notablement inférieure à celle du plasma, ce qui minimise donc la formation de noir de carbone. Les hydrocarbures insaturés obtenus par la réaction de conversion réalisée à l'intérieur du lit fluidisé sont ensuite évacués par le tube 5. Des thermocouples installés dans ce tube permettent de mesurer les températures.The plasma torch 6 injects a hydrogen plasma, which may contain argon and containing at least 10% hydrogen, into the fluidized particle bed where a homogeneous transfer of heat takes place between the plasma and fluidized bed , thus making it possible to carry out a conversion reaction in the presence of radical hydrogen at an adjusted temperature which remains notably lower than that of plasma, which therefore minimizes the formation of carbon black. The unsaturated hydrocarbons obtained by the reaction of conversion carried out inside the fluidized bed are then evacuated by tube 5. Thermocouples installed in this tube make it possible to measure the temperatures.
L'utilisation d'un lit fluidisé dans le procédé selon l'invention présente des avantages importants pour les raisons suivantes :
- ses propriétés de transfert de chaleur permettent une trempe efficace du plasma ;
- sa viscosité sensiblement égale à celle du plasma assure un très bon mélange entre celui-ci et le lit fluidisé ; et
- ses propriétés catalytiques éventuelles peuvent assurer la transformation directe du ou des produits à convertir en hydrocarbures insaturés.The use of a fluidized bed in the process according to the invention has significant advantages for the following reasons:
- its heat transfer properties allow efficient quenching of the plasma;
- Its viscosity substantially equal to that of the plasma ensures a very good mixture between it and the fluidized bed; and
- its possible catalytic properties can ensure the direct transformation of the product or products to be converted into unsaturated hydrocarbons.
D'autre part, la nature du matériau des particules constituant le lit et/ou la nature du catalyseur permettant d'orienter la conversion vers les produits souhaités.On the other hand, the nature of the material of the particles constituting the bed and / or the nature of the catalyst making it possible to direct the conversion towards the desired products.
Les huit exemples suivants sont donnés dans le but de bien mettre en évidence les avantages de la présente invention.The following eight examples are given in order to clearly demonstrate the advantages of the present invention.
D'une manière générale, les exemples ont été réalisés de la façon suivante :In general, the examples were carried out as follows:
La torche à plasma fonctionne à une fréquence de 5 MHz pour une puissance de 4,4 kW. L'angle d'injection est de 20°. Les gaz plasmagènes introduits sont de l'argon, à un débit de 30 l/min et de l'hydrogène à un débit de 5 l/min. Le lit est constitué de particules d'alumine (650g) de 300 microns de diamètre moyen. Les particules du lit sont mises en fluidisation par un mélange de méthane, d'hydrogène et d'argon. Par un ajustement du débit de ces trois gaz, on règle le temps de séjour du méthane dans le réacteur. Une bonne fluidisation est obtenue pour un débit total compris entre 15 l/min et 40 l/min. On détermine la quantité optimale d'hydrogène de fluidisation par rapport à celle du méthane de façon à minimiser la formation de noir de carbone. Ce rapport est compris entre 0,5 et 10 et de préférence entre 2 et 5. Les gaz de fluidisation sont préchauffés à une température comprise entre 50 et 500°C, de préférence entre 150°C et 350°C. Les débits de gaz plasmagènes et de fluidisation sont mesurés et régulés au moyen de débitmètres massiques. Des thermocouples sont installés pour permettre de mesurer la température des gaz de fluidisation en amont de l'enceinte, de la paroi de l'enceinte, du lit fluidisé et les températures dans le tube 5.The plasma torch operates at a frequency of 5 MHz for a power of 4.4 kW. The injection angle is 20 °. The plasma gases introduced are argon, at a flow rate of 30 l / min and hydrogen at a flow rate of 5 l / min. The bed is made of alumina particles (650g) of 300 microns in average diameter. The particles of the bed are put in fluidization by a mixture of methane, hydrogen and argon. By adjusting the flow rate of these three gases, the residence time of the methane in the reactor is adjusted. Good fluidization is obtained for a total flow of between 15 l / min and 40 l / min. The optimal amount of hydrogen fluidization is determined relative to that of methane so as to minimize the formation of carbon black. This ratio is between 0.5 and 10 and preferably between 2 and 5. The fluidization gases are preheated to a temperature between 50 and 500 ° C, preferably between 150 ° C and 350 ° C. The plasma gas and fluidization flow rates are measured and regulated using mass flow meters. Thermocouples are installed to measure the temperature of the fluidizing gases upstream of the enclosure, the wall of the enclosure, the fluidized bed and the temperatures in the tube 5.
La température du lit fluidisé est choisie comme température de référence puisque d'une part elle caractérise l'efficacité de la trempe et d'autre part parce que la réaction de conversion a lieu dans le lit fluidisé.The temperature of the fluidized bed is chosen as the reference temperature since on the one hand it characterizes the efficiency of the quenching and on the other hand because the conversion reaction takes place in the fluidized bed.
L'analyse des produits se fait par chromatographie en phase gazeuse.The analysis of the products is carried out by gas chromatography.
Les huit exemples sont détaillés dans les tableaux 1 et 2 suivants. Ils ont été effectués avec la même masse de particules identiques et avec des conditions de fonctionnement de la torche identiques. Ils diffèrent entre eux par les débits des gaz de fluidisation et par la température moyenne du lit fluidisé. Les résultats obtenus avec ces différents exemples sont également détaillés dans les tableaux 1 et 2 suivants.
Les résultats obtenus et listés dans les tableaux 1 et 2 montrent tout l'intérêt du procédé et prouvent particulièrement l'efficacité de la trempe par le lit fluidisé puisque la température moyenne dans celui-ci est relativement basse (comprise entre 500°C et 800°C).The results obtained and listed in Tables 1 and 2 show the advantage of the process and particularly prove the efficiency of quenching by the fluidized bed since the average temperature in it is relatively low (between 500 ° C and 800 ° C).
Les exemples 1 à 3 ont été effectués dans des conditions de fluidisation identiques mais à trois températures différentes. Les résultats montrent que la quantité de noir de carbone formée augmente très rapidement avec la température. Il ressort de ces résultats que le contrôle de la température est primordial et l'on comprend donc tout l'intérêt qu'il y a à tremper le plasma.Examples 1 to 3 were carried out under identical fluidization conditions but at three different temperatures. The results show that the amount of carbon black formed increases very rapidly with temperature. It emerges from these results that temperature control is essential and we therefore understand the advantage of soaking the plasma.
L'exemple 4 a été effectué à une température de 500°C. On remarque que le taux de conversion de CH₄ à cette température n'est que de 9%. En conséquence une température d'environ 500°C constitue la limite inférieure pour la conversion du méthane.Example 4 was carried out at a temperature of 500 ° C. Note that the conversion rate of CH₄ at this temperature is only 9%. Consequently a temperature of about 500 ° C constitutes the lower limit for the conversion of methane.
Les exemples 5 et 6 ont été effectués à une même température mais avec un débit de fluidisation différent. On constate une augmentation du taux de conversion lorsque le débit du gaz de fluidisation diminue, c'est-à-dire lorsque le temps de séjour du méthane augmente. Le contrôle de ce paramètre important peut donc se faire facilement.Examples 5 and 6 were carried out at the same temperature but with a different fluidization flow. There is an increase in the conversion rate when the flow rate of the fluidizing gas decreases, that is to say when the residence time of the methane increases. The control of this important parameter can therefore be done easily.
Si l'on compare les exemples 6 et 7, on note une nette augmentation du rendement en C2,due certainement à l'accroissement du rapport hydrogène/méthane. Le rôle de l'hydrogène de fluidisation est multiple. Notamment il inhibe les réactions de déshydrogénation conduisant au noir de carbone et il "protège" le méthane contre les chocs thermiques, mais il peut aussi limiter la réaction de conversion, d'où la nécessité de déterminer sa concentration optimale.If we compare Examples 6 and 7, we note a clear increase in the yield of C2, certainly due to the increase in the hydrogen / methane ratio. The role of hydrogen fluidization is manifold. In particular it inhibits the dehydrogenation reactions leading to carbon black and it "protects" the methane against thermal shocks, but it can also limit the conversion reaction, hence the need to determine its optimal concentration.
L'exemple 8 a été réalisé pour observer le rôle spécifique du plasma qui est d'apporter en forte concentration des espèces radicalaires. Pour ce faire, une expérience simple a été réalisée qui consiste à arrêter la torche et à analyser aussitôt le mélange réactionnel. On remarque qu'à une même température mais sans le plasma, le taux de conversion du méthane est négligeable.Example 8 was carried out to observe the specific role of plasma which is to provide in high concentration radical species. To do this, a simple experiment was carried out which consists in stopping the torch and immediately analyzing the reaction mixture. Note that at the same temperature but without the plasma, the methane conversion rate is negligible.
Bien que ces exemples aient été obtenus sans optimisation des paramètres opératoires, on remarquera les très bons résultats de l'exemple 7 dans lequel la sélectivité en C2 (acétylène) est de 94% c'est-à-dire déjà meilleure que celle du procédé Hüls qui est d'environ 74%.Although these examples were obtained without optimization of the operating parameters, it will be noted the very good results of Example 7 in which the selectivity for C2 (acetylene) is 94%, that is to say already better than that of the process Hüls which is around 74%.
La conversion du méthane est définie par le rapport de la quantité de méthane converti par la quantité totale de méthane introduite. Elle est calculée ainsi :
La sélectivité en C2 est le rapport de la quantité de produits en C2 obtenus par la quantité de produits de conversion. Elle est calculée ainsi :
Le rendement en C2 est défini par le rapport de la quantité de produits en C2 obtenue par la quantité de méthane introduite. Il est calculé ainsi
Bien entendu, l'invention n'est nullement limitée aux modes de réalisations décrits et illustrés qui ne sont donnés qu'à titre d'exemple. Ainsi, en fonction de la nature du catalyseur, de la charge et des conditions opératoires, il est possible d'obtenir des hydrocarbures supérieures à C₂. Par ailleurs, on pourrait introduire dans le lit fluidisé les produits à convertir, différemment de l'exemple représenté, c'est-à-dire séparément du gaz de fluidisation, à tout endroit approprié à condition de respecter la trempe du plasma par le lit fluidisé. Il est bien entendu également que le plasma utilisé peut être produit de façon quelconque, notamment par arc électrique soufflé ou transféré ou bien encore par induction.Of course, the invention is in no way limited to the embodiments described and illustrated which are given only by way of example. Thus, depending on the nature of the catalyst, the charge and the operating conditions, it is possible to obtain hydrocarbons greater than C₂. Furthermore, the products to be converted could be introduced into the fluidized bed, differently from the example shown, that is to say separately from the fluidization gas, at any suitable location provided that the quenching of the plasma by the bed is respected. fluidized. It is also understood that the plasma used can be produced in any manner, in particular by blown or transferred electric arc or even by induction.
Claims (13)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AT89403234T ATE86596T1 (en) | 1988-11-24 | 1989-11-22 | PROCESS FOR CONVERTING NATURAL GAS OR LIGHT ALKANES INTO UNSATURATED HYDROCARBONS. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR8815362A FR2639345B1 (en) | 1988-11-24 | 1988-11-24 | PROCESS FOR CONVERTING NATURAL GAS OR LIGHT ALKANES IN UNSATURATED HYDROCARBONS |
FR8815362 | 1988-11-24 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0370909A1 true EP0370909A1 (en) | 1990-05-30 |
EP0370909B1 EP0370909B1 (en) | 1993-03-10 |
Family
ID=9372212
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP89403234A Expired - Lifetime EP0370909B1 (en) | 1988-11-24 | 1989-11-22 | Process for the conversion of natural gas or of light alkanes into unsaturated hydrocarbons |
Country Status (10)
Country | Link |
---|---|
US (1) | US5053575A (en) |
EP (1) | EP0370909B1 (en) |
AT (1) | ATE86596T1 (en) |
AU (1) | AU614198B2 (en) |
CA (1) | CA2003620A1 (en) |
DE (1) | DE68905302D1 (en) |
ES (1) | ES2039912T3 (en) |
FR (1) | FR2639345B1 (en) |
NO (1) | NO894671L (en) |
NZ (1) | NZ231497A (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6130260A (en) * | 1998-11-25 | 2000-10-10 | The Texas A&M University Systems | Method for converting natural gas to liquid hydrocarbons |
US6602920B2 (en) * | 1998-11-25 | 2003-08-05 | The Texas A&M University System | Method for converting natural gas to liquid hydrocarbons |
US6500313B2 (en) | 2001-03-12 | 2002-12-31 | Steven P. Sherwood | Method for production of hydrocarbons |
US20050288541A1 (en) * | 2002-03-19 | 2005-12-29 | Sherwood Steven P | Gas to liquid conversion process |
AU2003214197A1 (en) * | 2002-03-19 | 2003-10-08 | Energy Technologies Group, Inc. | Gas to liquid conversion process |
JP2022508353A (en) | 2018-08-23 | 2022-01-19 | トランスフォーム マテリアルズ エルエルシー | Systems and methods for treating gases |
US11633710B2 (en) | 2018-08-23 | 2023-04-25 | Transform Materials Llc | Systems and methods for processing gases |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1323474A (en) * | 1962-06-04 | 1963-04-05 | American Cyanamid Co | Synthesis of acetylene by plasma jet |
FR2596046A2 (en) * | 1985-11-08 | 1987-09-25 | Inst Francais Du Petrole | Process for the thermal conversion of methane to higher molecular weight hydrocarbons |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1880189A (en) * | 1926-07-09 | 1932-09-27 | Gasoline Prod Co Inc | Manufacturing hydrocarbon products |
US3192280A (en) * | 1960-12-27 | 1965-06-29 | Exxon Research Engineering Co | Preferred method for supplying reactants to a resonating shock tube machine |
US4487683A (en) * | 1982-07-26 | 1984-12-11 | Combustion Engineering, Inc. | Acetylene from coal and an electric arc |
US4599474A (en) * | 1983-10-31 | 1986-07-08 | Chevron Research Company | Conversions of low molecular weight hydrocarbons to higher molecular weight hydrocarbons using a metal-containing catalyst |
US4704493A (en) * | 1983-10-31 | 1987-11-03 | Chevron Corporation | Conversions of low molecular weight hydrocarbons to higher molecular weight hydrocarbons using a metal compound-containing catalyst (II-A) |
US4704487A (en) * | 1983-10-31 | 1987-11-03 | Chevron Research Company | Conversions of low molecular weight hydrocarbons to higher molecular weight hydrocarbons using a metal compound-containing catalyst (IV-B) |
US4608444A (en) * | 1984-04-05 | 1986-08-26 | The Halcon Sd Group, Inc. | Process and accompanying catalysts for the hydroformylation of formaldehyde to glycol-aldehyde |
US4705908A (en) * | 1984-12-31 | 1987-11-10 | Gondouin Oliver M | Natural gas conversion process |
US4814533A (en) * | 1985-10-31 | 1989-03-21 | Chevron Research Company | Enhancing the production of aromatics in high temperature, high space velocity catalytic conversion of lower molecular weight hydrocarbons to higher molecular weight hydrocarbons |
FR2632965A1 (en) * | 1988-06-15 | 1989-12-22 | Shell Int Research | PROCESS FOR INCREASING THE MOLECULAR WEIGHT OF HYDROCARBONS AND / OR DERIVATIVES THEREOF |
-
1988
- 1988-11-24 FR FR8815362A patent/FR2639345B1/en not_active Expired - Lifetime
-
1989
- 1989-11-22 EP EP89403234A patent/EP0370909B1/en not_active Expired - Lifetime
- 1989-11-22 CA CA002003620A patent/CA2003620A1/en not_active Abandoned
- 1989-11-22 ES ES198989403234T patent/ES2039912T3/en not_active Expired - Lifetime
- 1989-11-22 US US07/440,301 patent/US5053575A/en not_active Expired - Fee Related
- 1989-11-22 DE DE8989403234T patent/DE68905302D1/en not_active Expired - Lifetime
- 1989-11-22 AT AT89403234T patent/ATE86596T1/en not_active IP Right Cessation
- 1989-11-23 NZ NZ231497A patent/NZ231497A/en unknown
- 1989-11-23 AU AU45522/89A patent/AU614198B2/en not_active Ceased
- 1989-11-23 NO NO89894671A patent/NO894671L/en unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1323474A (en) * | 1962-06-04 | 1963-04-05 | American Cyanamid Co | Synthesis of acetylene by plasma jet |
FR2596046A2 (en) * | 1985-11-08 | 1987-09-25 | Inst Francais Du Petrole | Process for the thermal conversion of methane to higher molecular weight hydrocarbons |
Also Published As
Publication number | Publication date |
---|---|
AU614198B2 (en) | 1991-08-22 |
EP0370909B1 (en) | 1993-03-10 |
ES2039912T3 (en) | 1993-10-01 |
CA2003620A1 (en) | 1990-05-24 |
DE68905302D1 (en) | 1993-04-15 |
FR2639345A1 (en) | 1990-05-25 |
NO894671D0 (en) | 1989-11-23 |
NO894671L (en) | 1990-05-25 |
AU4552289A (en) | 1990-05-31 |
US5053575A (en) | 1991-10-01 |
ATE86596T1 (en) | 1993-03-15 |
NZ231497A (en) | 1992-04-28 |
FR2639345B1 (en) | 1991-03-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP0542597B1 (en) | Thermal hydrocarbon pyrolysis process using an electric furnace | |
EP0370909B1 (en) | Process for the conversion of natural gas or of light alkanes into unsaturated hydrocarbons | |
EP0319369B1 (en) | Process and apparatus for the conversion of hydrocarbons | |
EP0292391A1 (en) | Hydrocracking process of a hydrocarbon feed, and apparatus for carrying out this process | |
EP2424818A1 (en) | Method for producing a powder including carbon, silicon and boron | |
FR2743007A1 (en) | CONTINUOUS PYROLYSIS AND DECOKING PROCESS APPLICABLE IN PARTICULAR TO THE PRODUCTION OF ACETYLENE | |
FR2705142A1 (en) | A method of regulating the thermal level of a solid in a heat exchanger having cylindrical plies of tubes. | |
EP0370910A1 (en) | Process for cracking a heavy hydrocarbon feedstock into lower boiling hydrocarbons, and apparatus for carrying out this process | |
EP0539270B1 (en) | Process for the thermal conversion of methane and reactor for this process | |
FR2641543A1 (en) | METHOD AND DEVICE FOR VAPOCRAQUING A HYDROCARBON WITH TWO ATOMS OF CARBON AT LEAST IN A CONVECTION-HEATED TUBULAR REACTION ZONE | |
EP0733609B1 (en) | Process for the thermal conversion of aliphatically saturated or unsaturated hydrocarbons in acetylenic hydrocarbons | |
CA2360896C (en) | Process for endothermic conversion of hydrocarbons, its uses and installation for implementation of this process | |
EP0323287B1 (en) | Process for the thermal conversion of methane into hydrocarbons with a higher molecular weight, and reactor to be used in this process | |
FR2507615A1 (en) | PROCESS FOR THE PRODUCTION OF GASEOUS MIXTURES BY PARTIAL OXIDATION | |
FR2639346A1 (en) | Process for the production of alpha -olefins | |
EP0457643B1 (en) | Process for the thermal conversion of methane and reactor to be used therefor | |
CA1313885C (en) | Thermal process for converting methane into hydrocarbon fuel of higher molecular weight, reactor for said process and construction method for said reactor | |
CH414567A (en) | Process for carrying out thermal reactions and apparatus for carrying out this process | |
FR2520354A1 (en) | PROCESS FOR THE METHANIZATION OF SOLID CARBON MATERIALS | |
CH622964A5 (en) | Process for starting or maintaining a chemical reaction which takes place on heating and reactor for its use | |
EP1041060B1 (en) | Process for the preparation of methylacetylene and propadiene | |
Tsutsumi | Vacuum process for the production of acetylene by partial combustion of light naphtha with oxygen | |
BE834245A (en) | WALL REACTOR PROTECTED BY A FLUID, FOR CHEMICAL REACTIONS AT HIGH TEMPERATURE | |
FR2676222A1 (en) | Process for the dehydrogenation of aliphatic hydrocarbons to olefinic hydrocarbons | |
FR2676745A1 (en) | Catalytic process for the production of liquid hydrocarbons from natural gas |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE ES GB GR IT LI LU NL SE |
|
17P | Request for examination filed |
Effective date: 19901116 |
|
17Q | First examination report despatched |
Effective date: 19920526 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE ES GB GR IT LI LU NL SE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Effective date: 19930310 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 19930310 Ref country code: GB Effective date: 19930310 Ref country code: DE Effective date: 19930310 Ref country code: AT Effective date: 19930310 |
|
REF | Corresponds to: |
Ref document number: 86596 Country of ref document: AT Date of ref document: 19930315 Kind code of ref document: T |
|
REF | Corresponds to: |
Ref document number: 68905302 Country of ref document: DE Date of ref document: 19930415 |
|
ITF | It: translation for a ep patent filed |
Owner name: DE DOMINICIS & MAYER S.R.L. |
|
NLV1 | Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act | ||
GBV | Gb: ep patent (uk) treated as always having been void in accordance with gb section 77(7)/1977 [no translation filed] |
Effective date: 19930310 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2039912 Country of ref document: ES Kind code of ref document: T3 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SE Effective date: 19931123 Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19931123 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 19931130 Ref country code: LI Effective date: 19931130 Ref country code: CH Effective date: 19931130 Ref country code: BE Effective date: 19931130 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
BERE | Be: lapsed |
Owner name: GAZ DE FRANCE Effective date: 19931130 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
EUG | Se: european patent has lapsed |
Ref document number: 89403234.1 Effective date: 19940610 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 19941214 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED. Effective date: 20051122 |